A residue hydrotreating catalyst and a method for preparing the same

Abstract

This invention discloses a catalyst for the hydrotreating of residual oil and its preparation method, belonging to the field of catalytic materials technology. The preparation method includes: S1. Mixing dolomite, cerium carbonate, zirconium oxide precursors with a silica precursor, followed by drying and calcination to obtain a composite support. In-situ pore-forming is achieved using the gas generated from the decomposition of dolomite and cerium carbonate, forming a mesoporous structure; S2. Impregnating the composite support in a modification solution containing chitosan and mannouronic acid, and constructing a cross-linked network coating on its surface via a Schiff base reaction to obtain a modified support; S3. Impregnating the modified support in a precursor solution containing nickel, molybdenum, and sulfur sources, followed by adsorption, drying, and calcination to obtain the catalyst. This invention achieves high dispersion and stable loading of active metal components while obtaining a high-porosity support with suitable pore distribution through the synergistic effect of pore structure regulation and surface modification. The catalyst exhibits excellent hydrodesulfurization, denitrification, and demetallization performance in the hydrotreating of residual oil.

Description

Technical Field

[0001] This invention belongs to the field of catalytic materials technology, and particularly relates to a catalyst for the hydrotreating of residual oil and its preparation method. Background Technology

[0002] Residue hydrotreating technology is one of the core processes for achieving clean and efficient conversion of heavy residue oil. This technology, under high hydrogen partial pressure, effectively removes impurities such as sulfur, nitrogen, and metals from residue oil through catalysis, while simultaneously saturating some aromatics and cracking large molecules, thereby producing cleaner and higher-value light distillate oils. Compared with traditional coking processes, residue hydrotreating technology offers advantages such as higher liquid product yield, better product quality, and superior environmental benefits.

[0003] However, the residue hydrotreating process faces an extremely complex reaction environment. The reactants are a complex mixture containing large amounts of asphaltenes, gums, and polycyclic aromatic hydrocarbons (PAHs). The reaction process is the result of multiple steps, including diffusion and mass transfer of reactant molecules within the catalyst channels, adsorption at active sites, surface chemical reactions, and product desorption. Among these, catalyst performance is the core factor determining the overall techno-economic indicators of the process. High-performance residue hydrotreating catalysts need to meet two seemingly contradictory but synergistically optimized key structural requirements: First, they need sufficiently large pore sizes and suitable pore size distributions. This ensures that the bulky asphaltenes and other macromolecules in the residue can diffuse smoothly into the catalyst particles and contact the internal surface active sites, thus avoiding premature catalyst deactivation due to rapid coking and blockage at the pore openings, and fully utilizing the overall catalyst volume. Second, they need sufficiently high specific surface areas and abundant surface active sites. This is to load the hydrotreating active metal components with high density and high dispersion, forming an appropriately sized and fully exposed active phase, thereby providing sufficient intrinsic catalytic activity.

[0004] In traditional catalyst preparation, increasing pore size often comes at the cost of sacrificing specific surface area, while pursuing high specific surface area usually results in smaller pore sizes. This intrinsic contradiction between pore structure and active sites severely restricts further improvement in the overall performance of the catalyst. Furthermore, achieving high dispersion and effective stability of active metal components on macroporous supports, preventing sintering and aggregation during preparation or use, is also a technical challenge. Commonly used impregnation methods are prone to uneven distribution and local aggregation of active metals due to factors such as uneven surface properties of the support or surface tension of the impregnation liquid, affecting the formation efficiency of the active phase and the final catalytic performance. Therefore, it is essential to develop a novel preparation method that can precisely and synergistically control the macroscopic pore structure of the catalyst to optimize mass transfer and simultaneously achieve high dispersion and stable loading of active components at the microscale. Summary of the Invention

[0005] In order to overcome the shortcomings of the prior art, the present invention prepares a residue oil hydrotreating catalyst with high porosity and suitable pore distribution, which enables the catalyst to exhibit excellent hydrodesulfurization, denitrification and demetallization performance during residue oil hydrotreating.

[0006] To achieve the above objectives, the following technical solution is adopted: This invention provides a method for preparing a catalyst for the hydrotreating of residual oil, comprising the following steps:

[0007] S1. Mix dolomite, cerium carbonate, zirconium oxide precursor with silica precursor, and after mixing, dry and calcine to obtain zirconium oxide / silica composite carrier;

[0008] S2. The zirconium oxide / silica composite carrier is impregnated in a modification solution containing chitosan and mannouric acid, and after ultrasonic vibration and heat treatment, a modified zirconium oxide / silica carrier is obtained.

[0009] S3. The modified zirconium oxide / silica support is impregnated in a precursor solution containing nickel, molybdenum and sulfur sources, and after adsorption, drying and calcination, the residue oil hydrotreating catalyst is obtained.

[0010] Further, in step S1, the zirconium oxide precursor is one of zirconium oxychloride or zirconium oxynitrate, the silica precursor is one of silica sol or tetraethyl orthosilicate, and the mass ratio of the zirconium oxide precursor to the silica precursor is 10-30:60-85.

[0011] Further, in step S1, the amount of dolomite added is 5-15 wt% of the total mass of the zirconium oxide / silica composite carrier raw material, and the amount of cerium carbonate added is 1-5 wt% of the total mass of the zirconium oxide / silica composite carrier raw material.

[0012] Further, in step S1, the calcination conditions are as follows: in an air atmosphere, the temperature is increased to 500-700℃ at a rate of 2-5℃ / min, and calcined at a constant temperature for 3-6 hours.

[0013] Further, in step S2, the mass-to-volume ratio of the zirconium oxide / silica carrier to the modified liquid is 1g:10-15mL, the mass ratio of chitosan to mannouronic acid in the modified liquid is 1-3:1, and the total mass concentration of the two is 2-6wt%; the solvent of the modified liquid is an aqueous solution of acetic acid with a mass fraction of 1-3%.

[0014] Further, in step S2, the ultrasonic oscillation conditions are: constant temperature oscillation and immersion at 40-60℃ for 2-4 hours, and the heat treatment conditions are: treatment at 100-150℃ for 6-10 hours.

[0015] Further, in step S3, the nickel source is either nickel nitrate or nickel sulfate, the molybdenum source is ammonium molybdate, and the sulfur source is either thiourea or ammonium sulfide. The amounts of the nickel source, molybdenum source, and sulfur source are based on the mass of the modified zirconia / silica support, wherein the nickel loading is 0.5-1.9 mmol / g support, the molybdenum loading is 0.8-3.2 mmol / g support, and the sulfur loading is 1.9-6.8 mmol / g support.

[0016] Further, in step S3, the solvent of the precursor solution is a mixed solution of deionized water and ethanol in a volume ratio of 1:0.8-3; the mass-volume ratio of the modified zirconium oxide / silica support to the precursor solution is 1g:8-12mL.

[0017] Further, in step S3, the impregnation conditions are:

[0018] The temperature is 50-60℃, the oscillation frequency is 100-300r / min, and the impregnation time is 8-12h. The calcination conditions are as follows: under the protection of inert gas, the temperature is first raised to 100-300℃ at 1-5℃ / min and held for 1h, then raised to 400-450℃ and held for 1-3h, and finally raised to 500-550℃ and held for 3-4h.

[0019] The present invention also provides a catalyst for the hydrotreating of residual oil, which is prepared according to the preparation method described above.

[0020] The beneficial effects of this invention are:

[0021] The residue hydrotreating catalyst prepared by this invention possesses high porosity and a suitable pore distribution, which facilitates the diffusion of large residue molecules. Simultaneously, the highly dispersed, small-sized active metal phase provides abundant catalytic active centers, as well as enhanced active phase formation efficiency and stability. These characteristics work together to enable the catalyst to exhibit excellent hydrodesulfurization, denitrification, and demetallization performance during residue hydrotreating.

[0022] This invention utilizes the decomposition of dolomite and cerium carbonate during calcination to generate gases such as CO2. This process acts as an in-situ pore-forming agent in the zirconium oxide / silica composite system, promoting the formation of a well-connected mesoporous structure on the support. This significantly increases the specific surface area and porosity of the support, providing an effective diffusion channel for macromolecular reactants in the residue oil, alleviating internal diffusion limitations, and enhancing reaction accessibility. Simultaneously, cerium enters the support framework or is highly dispersed on the surface in the form of CeO2, which can regulate the local electronic environment on the support surface and enhance the support's affinity for heteroatoms such as sulfur and nitrogen. This provides a potential activity-promoting effect for subsequent hydrodesulfurization, hydrodenitrification, and other reactions.

[0023] This invention further utilizes the Schiff base reaction between the amino groups on the chitosan chain and the aldehyde groups on the mannuronic acid chain under mild conditions to construct an organic polymer coating with a cross-linked network structure on the support surface. This network is rich in amino and carboxyl groups, which can serve as multifunctional coordination sites. When impregnating active metal precursors, these functional groups can effectively anchor nickel and molybdenum metal ions through coordination, electrostatic attraction, or hydrogen bonding, enabling them to achieve uniform adsorption at the molecular level on the support surface. This avoids the problem of metal aggregation caused by surface energy differences in traditional impregnation methods. During the subsequent calcination process, the organic network is gradually decomposed and removed, but the metal ions it fixes are already highly dispersed beforehand, thus promoting a more uniform distribution of the final catalyst, exposing more active sites, and significantly improving the catalytic efficiency of the active phase. Attached Figure Description

[0024] Figure 1 This is a process flow diagram of a method for preparing a catalyst for the hydrotreating of residual oil according to the present invention;

[0025] Figure 2 The isothermal adsorption curve of the modified zirconium oxide / silica support prepared in Example 2 of this invention;

[0026] Figure 3 This is an XRD image of the catalyst prepared in Example 2 of the present invention.

[0027] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the embodiments of the invention to explain the invention and do not constitute a limitation thereof. Detailed Implementation

[0028] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those familiar to those skilled in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to this invention. The preferred embodiments and materials described herein are for illustrative purposes only and do not limit the scope of this application.

[0030] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, and the experimental materials used in the following embodiments are commercially available. The process flow diagram of the preparation method of the residue hydrotreating catalyst in the following embodiments of the present invention is attached. Figure 1 As shown.

[0031] Example 1

[0032] A method for preparing a catalyst for the hydrotreating of residual oil includes the following steps:

[0033] S1. Dolomite, cerium carbonate, zirconium oxide precursor, and silica precursor are mixed, wherein the zirconium oxide precursor is zirconium oxychloride, the silica precursor is silica sol, and the mass ratio of zirconium oxide precursor to silica precursor is 10:60; the amount of dolomite added is 5 wt% of the total mass of the carrier raw materials, and the amount of cerium carbonate added is 1 wt% of the total mass of the carrier raw materials; after mixing, the mixture is dried and calcined to obtain a zirconium oxide / silica composite carrier. The calcination conditions are: heating to 500°C at a rate of 2°C / min in air atmosphere and calcining at a constant temperature for 3 hours.

[0034] S2. The zirconium oxide / silica composite carrier is impregnated in a modification solution containing chitosan and mannouric acid, wherein the mass-to-volume ratio of the zirconium oxide / silica carrier to the modification solution is 1:10 (g / mL), the mass ratio of chitosan to mannouric acid is 1:1, and the total mass concentration of both is 2wt%; the solvent of the modification solution is a 1% (w / w) aqueous solution of acetic acid; after ultrasonic vibration and heat treatment, the modified zirconium oxide / silica carrier is obtained, wherein the ultrasonic vibration conditions are: constant temperature vibration impregnation at 40℃ for 2h, and the heat treatment conditions are: treatment at 100℃ for 6h;

[0035] S3. The modified zirconia / silica support is immersed in a precursor solution containing a nickel source, a molybdenum source, and a sulfur source, wherein the nickel source is nickel nitrate, the molybdenum source is ammonium molybdate, and the sulfur source is thiourea. The amounts of the nickel, molybdenum, and sulfur sources are based on the mass of the modified zirconia / silica support, wherein the nickel loading is 0.5 mmol / g support, the molybdenum loading is 0.8 mmol / g support, and the sulfur loading is 1.9 mmol / g support; the solvent of the precursor solution is deionized water and ethanol. A mixed solution of alcohol in a volume ratio of 1:1; the mass-to-volume ratio of the modified zirconium oxide / silica support to the precursor solution is 1:8 (g / mL); the impregnation conditions are: temperature 50℃, oscillation frequency 150r / min, and impregnation time 8h; after adsorption, drying, and calcination, the catalyst for hydrotreating the residue oil is obtained. The calcination conditions are: under inert gas protection, first, the temperature is increased to 200℃ at 4℃ / min and held for 1h, then increased to 400℃ and held for 2h, and finally increased to 500℃ and held for 3h.

[0036] Example 2

[0037] A method for preparing a catalyst for the hydrotreating of residual oil includes the following steps:

[0038] S1. Dolomite, cerium carbonate, zirconium oxide precursor, and silica precursor are mixed, wherein the zirconium oxide precursor is zirconium oxynitrate, the silica precursor is tetraethyl orthosilicate, and the mass ratio of the zirconium oxide precursor to the silica precursor is 30:85; the amount of dolomite added is 15 wt% of the total mass of the carrier raw materials, and the amount of cerium carbonate added is 5 wt% of the total mass of the carrier raw materials; after mixing, the mixture is dried and calcined, wherein the calcination conditions are as follows: in an air atmosphere, a zirconium oxide / silica composite carrier is obtained, heated to 700°C at a rate of 5°C / min, and calcined at a constant temperature for 6 hours;

[0039] S2. The zirconium oxide / silica composite carrier is impregnated in a modification solution containing chitosan and mannouric acid, wherein the mass-to-volume ratio of the zirconium oxide / silica carrier to the modification solution is 1:15 (g / mL), the mass ratio of chitosan to mannouric acid is 3:1, and the total mass concentration of the two is 4wt%; the solvent of the modification solution is a 3% (w / w) aqueous solution of acetic acid; after ultrasonic vibration and heat treatment, the modified zirconium oxide / silica carrier is obtained, wherein the ultrasonic vibration conditions are: constant temperature vibration impregnation at 60℃ for 4h, and the heat treatment conditions are: treatment at 150℃ for 10h;

[0040] S3. The modified zirconia / silica support is immersed in a precursor solution containing a nickel source, a molybdenum source, and a sulfur source, wherein the nickel source is nickel sulfate, the molybdenum source is ammonium molybdate, and the sulfur source is ammonium sulfide. The amounts of the nickel, molybdenum, and sulfur sources are based on the mass of the modified zirconia / silica support, wherein the nickel loading is 1.9 mmol / g support, the molybdenum loading is 3.2 mmol / g support, and the sulfur loading is 6.8 mmol / g support; the solvent of the precursor solution is deionized water and ethanol. A mixed solution with an alcohol volume ratio of 1:1; the mass-to-volume ratio of the modified zirconium oxide / silica support to the precursor solution is 1:12 (g / mL); the impregnation conditions are: temperature 60℃, oscillation frequency 150r / min, and impregnation time 12h; after adsorption, drying, and calcination, the residue oil hydrotreating catalyst is obtained. The calcination conditions are: under inert gas protection, first, the temperature is increased to 200℃ at 4℃ / min and held for 1h, then increased to 450℃ and held for 2h, and finally increased to 550℃ and held for 4h.

[0041] Example 3

[0042] A method for preparing a catalyst for the hydrotreating of residual oil includes the following steps:

[0043] S1. Dolomite, cerium carbonate, zirconium oxide precursor, and silica precursor are mixed, wherein the zirconium oxide precursor is zirconium oxychloride, the silica precursor is tetraethyl orthosilicate, and the mass ratio of the zirconium oxide precursor to the silica precursor is 20:72.5; the amount of dolomite added is 10 wt% of the total mass of the carrier raw materials, and the amount of cerium carbonate added is 3 wt% of the total mass of the carrier raw materials; after mixing, the mixture is dried and calcined to obtain a zirconium oxide / silica composite carrier. The calcination conditions are: heating to 600℃ at a rate of 3.5℃ / min in air atmosphere and calcining at a constant temperature for 4.5h;

[0044] S2. The zirconium oxide / silica composite carrier is impregnated in a modification solution containing chitosan and mannouric acid, wherein the mass-to-volume ratio of the zirconium oxide / silica carrier to the modification solution is 1:12.5 (g / mL), the mass ratio of chitosan to mannouric acid is 2:1, and the total mass concentration of the two is 6wt%; the solvent of the modification solution is a 2% (w / w) aqueous solution of acetic acid; after ultrasonic vibration and heat treatment, the modified zirconium oxide / silica carrier is obtained, wherein the ultrasonic vibration conditions are: constant temperature vibration impregnation at 50℃ for 3h, and the heat treatment conditions are: treatment at 125℃ for 8h;

[0045] S3. The modified zirconia / silica support is immersed in a precursor solution containing a nickel source, a molybdenum source, and a sulfur source, wherein the nickel source is nickel nitrate, the molybdenum source is ammonium molybdate, and the sulfur source is thiourea. The amounts of the nickel, molybdenum, and sulfur sources are based on the mass of the modified zirconia / silica support, wherein the nickel loading is 1.2 mmol / g support, the molybdenum loading is 2.0 mmol / g support, and the sulfur loading is 3.5 mmol / g support; the solvent of the precursor solution is deionized water and ethanol. A mixed solution with a volume ratio of 1:1; the mass-to-volume ratio of the modified zirconium oxide / silica support to the precursor solution is 1:10 (g / mL); the impregnation conditions are: temperature 55℃, oscillation frequency 150r / min, and impregnation time 10h; after adsorption, drying, and calcination, the residue oil hydrotreating catalyst is obtained. The calcination conditions are: under inert gas protection, first, the temperature is raised to 200℃ at 4℃ / min and held for 1h, then raised to 425℃ and held for 2h, and finally raised to 525℃ and held for 3.5h.

[0046] Comparative Example 1

[0047] The preparation method of this comparative example is basically the same as that of Example 3, except that in step S1, dolomite and cerium carbonate are not added. Instead, the zirconium oxide precursor and the silica precursor are mixed, dried, and calcined to obtain an undoped zirconium oxide / silica composite support. The remaining components, component ratios, and steps are exactly the same as in Example 3.

[0048] Comparative Example 2

[0049] The preparation method of this comparative example is basically the same as that of Example 3, but step S2 is omitted. That is, the zirconium oxide / silicon oxide composite support obtained in step S1 of Example 3 is directly used for active metal impregnation loading in step S3. The remaining components, component ratios, and steps are exactly the same as those in Example 3.

[0050] Comparative Example 3

[0051] This comparative example uses a conventional co-impregnation method to prepare the catalyst. The γ-Al2O3 support is directly impregnated in a precursor solution containing nickel nitrate, ammonium molybdate, and thiourea for 12 hours at room temperature. Subsequently, it is filtered, dried, and calcined at 500°C for 4 hours in air to obtain the Ni-Mo-S / Al2O3 catalyst prepared by the conventional method.

[0052] Results Analysis

[0053] Figure 2 The isothermal adsorption curves of the modified zirconium oxide / silica support prepared in Example 2 are shown below. Figure 2 As can be seen from the data, the carrier is a typical mesoporous material with good pore connectivity, which is conducive to the diffusion of reactants and products.

[0054] The catalyst prepared in Example 2 was tested using X-ray diffraction, and the results are as follows: Figure 3 As shown, Figure 3 The diffraction peaks at 34°, 38°, 59°, and 69° represent CeO2, MoO3, NiO, and S, respectively, indicating that the catalyst was successfully loaded with molybdenum oxide (MoO3), nickel oxide (NiO), elemental sulfur (S), and cerium oxide (CeO2).

[0055] The physicochemical properties of the catalysts prepared in each example and comparative example were characterized, and the results are shown in Table 1.

[0056] Table 1. Characterization Results of Physicochemical Properties of Catalysts

[0057]

[0058] The catalysts prepared in each example and comparative example were subjected to residue hydrotreating evaluation experiments using vacuum residue with the following properties: sulfur content 3.85 wt%, nitrogen content 0.42 wt%, and total nickel and vanadium content 125 μg / g. The reaction was conducted in a fixed-bed microreactor. The reaction temperature was 380 °C, the hydrogen partial pressure was 12.0 MPa, the hydrogen-to-oil volume ratio was 800:1, and the volume hourly space velocity was 1.0 h⁻¹. -1After the reaction stabilized for 24 hours, samples were taken for analysis of the generated oil. Sulfur content was determined by ultraviolet fluorescence, nitrogen content by chemiluminescence, and total metal (nickel, vanadium) content by ICP-AES. Hydrodesulfurization rate (HDS), hydrodenitrogenation rate (HDN), and demetallization rate (HDM) were calculated. The results are shown in Table 2.

[0059] Table 2. Evaluation Results of Catalyst Residue Hydrotreating Performance

[0060]

[0061] As shown in Table 1, the catalysts in Examples 1-3 all exhibited high specific surface area and large pore volume, with moderate average pore size. In contrast, the specific surface area and pore volume of Comparative Example 1 decreased significantly, and the average pore size decreased. This indicates that the dolomite and cerium carbonate added in this invention decompose to generate gas during calcination, effectively creating pores in situ and successfully constructing a mesoporous structure conducive to macromolecular diffusion. This is directly reflected in the fact that the HDS, HDN, and HDM activities of Comparative Example 1 are all lower than those of all other examples, especially in the larger molecular size of the dismetallization reaction (HDM), confirming the key role of optimizing the pore structure in alleviating internal diffusion limitations and improving the accessibility of macromolecules in residual oil. The metal dispersion of Examples 1-3 was high, and the Ni-Mo-S active phase grain size was small. Although Comparative Example 2 had similar pore structure parameters to Example 3, its metal dispersion was significantly reduced, and the active phase grain size increased. This indicates that omitting the surface modification step prevents the active metal precursor from being effectively anchored and dispersed on the support surface, leading to easier aggregation during calcination. This microstructural disadvantage directly results in the catalytic activity of Comparative Example 2 being significantly lower than that of the embodiments of the present invention. Comparative Example 3 exhibits inferior physicochemical properties compared to the embodiments of the present invention, with the largest active phase grain size. Under the same reaction conditions, its hydrodesulfurization, denitrification, and demetallization performance is the worst among all samples. This fully demonstrates that the catalyst prepared by the method of constructing a mesoporous support through in-situ pore creation and anchoring with an organic network to achieve high metal dispersion in the present invention achieves optimization in both pore structure and active centers, resulting in significantly superior overall performance compared to traditional catalyst preparation methods.

[0062] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

[0063] The present invention and its embodiments have been described above. This description is not restrictive, and the embodiments shown are only one of the embodiments of the present invention. The actual application is not limited to this. In conclusion, if those skilled in the art are inspired by this description and design similar methods and embodiments without departing from the spirit of the present invention, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a catalyst for the hydrotreating of residual oil, characterized in that: Includes the following steps: S1. Mix dolomite, cerium carbonate, zirconium oxide precursor with silica precursor, and after mixing, dry and calcine to obtain zirconium oxide / silica composite carrier; S2. The zirconium oxide / silica composite carrier is impregnated in a modification solution containing chitosan and mannouric acid, and after ultrasonic vibration and heat treatment, a modified zirconium oxide / silica carrier is obtained. S3. The modified zirconium oxide / silica support is impregnated in a precursor solution containing nickel, molybdenum and sulfur sources, and after adsorption, drying and calcination, the residue oil hydrotreating catalyst is obtained.

2. The method for preparing the residue hydrotreating catalyst according to claim 1, characterized in that: In step S1, the zirconium oxide precursor is one of zirconium oxychloride or zirconium oxynitrate, the silica precursor is one of silica sol or tetraethyl orthosilicate, and the mass ratio of the zirconium oxide precursor to the silica precursor is 10-30:60-85.

3. The method for preparing the catalyst for hydrotreating residual oil according to claim 1, characterized in that: In step S1, the amount of dolomite added is 5-15 wt% of the total mass of the zirconium oxide / silicon oxide composite carrier raw material, and the amount of cerium carbonate added is 1-5 wt% of the total mass of the zirconium oxide / silicon oxide composite carrier raw material.

4. The method for preparing the catalyst for hydrotreating residual oil according to claim 1, characterized in that: In step S1, the calcination conditions are as follows: in an air atmosphere, the temperature is increased to 500-700℃ at a rate of 2-5℃ / min, and then calcined at a constant temperature for 3-6 hours.

5. The method for preparing the residue hydrotreating catalyst according to claim 1, characterized in that: In step S2, the mass-to-volume ratio of the zirconium oxide / silica composite carrier to the modified liquid is 1g:10-15mL, the mass ratio of chitosan to mannouronic acid in the modified liquid is 1-3:1, and the total mass concentration of the two is 2-6wt%; the solvent of the modified liquid is an aqueous solution of acetic acid with a mass fraction of 1-3%.

6. The method for preparing the catalyst for hydrotreating residual oil according to claim 1, characterized in that: In step S2, the ultrasonic oscillation conditions are: constant temperature oscillation and immersion at 40-60℃ for 2-4 hours, and the heat treatment conditions are: treatment at 100-150℃ for 6-10 hours.

7. The method for preparing the catalyst for hydrotreating residual oil according to claim 1, characterized in that: In step S3, the nickel source is either nickel nitrate or nickel sulfate, the molybdenum source is ammonium molybdate, and the sulfur source is either thiourea or ammonium sulfide. The amounts of the nickel, molybdenum, and sulfur sources are based on the mass of the modified zirconia / silica support, wherein the nickel loading is 0.5-1.9 mmol / g support, the molybdenum loading is 0.8-3.2 mmol / g support, and the sulfur loading is 1.9-6.8 mmol / g support.

8. The method for preparing the catalyst for hydrotreating residual oil according to claim 1, characterized in that: In step S3, the solvent of the precursor solution is a mixed solution of deionized water and ethanol in a volume ratio of 1:0.8-3; the mass-volume ratio of the modified zirconium oxide / silica support to the precursor solution is 1g:8-12mL.

9. The method for preparing the catalyst for hydrotreating residual oil according to claim 1, characterized in that: In step S3, the impregnation conditions are: temperature 50-60℃, oscillation frequency 100-300r / min, and impregnation time 8-12h; the calcination conditions are: under inert gas protection, first raise the temperature to 100-300℃ at 1-5℃ / min and hold for 1h, then raise the temperature to 400-450℃ and hold for 1-3h, and finally raise the temperature to 500-550℃ and hold for 3-4h.

10. A catalyst for the hydrotreating of residual oil, characterized in that: Prepared by the preparation method according to any one of claims 1-9.

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